CN103572583B - Aramid fiber coated with inorganic nanoparticles on surface and preparation method thereof - Google Patents
Aramid fiber coated with inorganic nanoparticles on surface and preparation method thereof Download PDFInfo
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- CN103572583B CN103572583B CN201310575472.5A CN201310575472A CN103572583B CN 103572583 B CN103572583 B CN 103572583B CN 201310575472 A CN201310575472 A CN 201310575472A CN 103572583 B CN103572583 B CN 103572583B
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Abstract
The invention relates to aramid fiber coated with inorganic nanoparticles on the surface and a preparation method thereof. The preparation method comprises the following steps: functionalizing the surface of the aramid fiber to enable the surface of the fiber to contain methoxy groups; hydroxylating calcium-oxide-doped cerium oxide and reacting the cerium oxide with the fiber to obtain the aramid fiber coated with the inorganic nanoparticles on the surface. According to the invention, the hydroxylated calcium-oxide-doped cerium oxide is an inorganic particle with the photocatalytic activity much lower than that of ultraviolet absorbents such as TiO2 and zinc oxide; the inorganic particles can absorb ultraviolet rays to protect the fiber from damage caused by the ultraviolet rays, and the damage caused by a photocatalytic action of the inorganic particles to the fiber during ultraviolet radiation can be avoided, so that the hydroxylated calcium-oxide-doped cerium oxide is a safe, effective and long-lasting ultraviolet absorber. The surface of the modified aramid fiber is provided with a large number of reactive groups, so that adhesion of the modified aramid fiber to a lot of substrates can be improved, and thus the application field of the fiber is widened; the nanoparticles with high heat resistance are coated on the surface of the fiber, so that the thermal property of the fiber can be effectively improved.
Description
Technical field
The present invention relates to a kind of modification technology of organic fiber, be specifically related to aramid fiber of a kind of Surface coating inorganic nano-particle and preparation method thereof.
Background technology
In world's chemical fiber hairs exhibition history, the invention of aramid fiber (PPTA) fiber is another landmark invention after polyamide fibre.Aramid fiber is with the low (1.43-1.44g/cm of density
3), intensity high (3.6 GPa), good toughness and high temperature resistant (500 DEG C) famous, it is not only widely used as the products for civilian use such as tire cord, Anti-cut Gloves, electronic apparatus, sports equipment, and also played important effect in Aero-Space, the military field such as shellproof, be referred to as " armoring bodyguard ".
But aramid fiber exists two major features, one is surface inertness, lacks active group, low (39.8 mJ/m of surface free energy
2), with the adhesiveness of resin and wettability poor, cause that the interlaminar shear strength of composite is low, hygroscopicity is poor, thus affect the performance of composites.Two is that ultra-violet resistance can be poor, and ultraviolet irradiation can cause fiber amido link to rupture, and occurs aging, fiber combination property (especially mechanical property) deterioration, and the phase of being on active service shortens.Therefore, since aramid fiber comes out, how to have overcome the important content that this two large shortcoming is just aramid fiber research and development always.
In recent years, for ultra-violet resistance energy and surface-activity, expand the research of a large amount of aramid fiber.Wherein, for improving surface-activity, mainly chemic modified method, namely in aramid fiber surface grafting or introduce chemical segment.For the research of ultra-violet resistance energy, mainly grafting or the coated inorganic particulate with high ultraviolet absorption ability.And about improving ultra-violet resistance energy and the rarely seen report of surface-active work simultaneously.
At present, the inorganic particulate for improving aramid fiber ultra-violet resistance energy has TiO
2and ZnO, but all there is very high photocatalytic activity in these two kinds of inorganic nano-particles, the performance of can degrade while improving fiber ultra-violet resistance energy organic fiber, deteriorated fiber.On the other hand, in existing technology, also there is other deficiencies.Such as, the people such as Ding adopts sol-gal process to synthesize TiO
2modification of aramid fiber is (see Xing YJ, Ding X. UV photo-stabilization of tetrabutyl titanate for aramid fibers via sol – gel surface modification. Journal of Applied Polymer Science, 2007, 103:3113 – 3119), because nano particle is formed in the dry run of fiber, so forming temperature is lower, crystallinity is bad, though the modified fibre obtained has be better than fibriilar ultra-violet resistance energy, but the stretching strength retentivity of modified fibre after 24h ultraviolet irradiation be not high (78.6%) still.In addition, TiO
2and lack chemical bonding between aramid fiber, be in use easy to come off.The people such as Phaneshwar adopt containing 5%TiO
2with the acrylate coatings Modified K evlar fabric of ZnO (see Phaneshwar K, Patra PK, Warner SB. Nanostructured ultraviolet resistant polymer coatings. Polymer Degradation and Stability, 2006,91:2437-2442), resistant fiber tearing strength conservation rate after 24h ultraviolet irradiation is brought up to 81% from 79%, and increase rate is little.On the other hand, containing double bond in acrylate, ultraviolet can accelerate that it is aging, and organicly agingly will make TiO
2peel off with ZnO.
Therefore, on the basis with former aramid fiber excellent heat resistance and mechanical property, study a kind of excellent resistance to ultraviolet, surface-active aramid fiber and preparation method thereof of having concurrently and there is important using value.
Summary of the invention
Can poor, problem that activity is low for solving ultra-violet resistance that prior art aramid fiber exists, the object of the present invention is to provide one not only to have former aramid fiber excellent heat resistance and mechanical property, and have excellent resistance to ultraviolet, surface-active modification of aramid fiber and preparation method thereof simultaneously concurrently.
The technical scheme realizing the object of the invention is to provide a kind of aramid fiber of Surface coating inorganic nano-particle, and inorganic nano-particle is coated on aramid fiber surface with the form of chemical bond, and the chemical formula of described inorganic nano-particle is Ce
1-xca
xo
2-x, wherein, x=0.1 ~ 0.5.
Technical solution of the present invention also provides a kind of preparation method of aramid fiber of Surface coating inorganic nano-particle, comprises the steps:
(1) by weight, 1 part of aramid fiber is immersed in reactant liquor, described reactant liquor comprises 100 ~ 200 parts of inorganic bases and 800 ~ 950 parts of alcohol or deionized water, be react under the condition of 40 ~ 80 DEG C in temperature, reaction terminates rear taking-up fiber, through cleaning, dry, obtain being with amino aramid fiber;
(2) under atmosphere of inert gases, by weight, the aramid fiber of 1 part of band amino, 200 ~ 400 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes and 1000 ~ 1500 parts of organic solvents are placed in reaction vessel, be react 10 ~ 20h under the condition of 50 ~ 100 DEG C in temperature, obtain the aramid fiber being with methoxyl group;
(3) by weight, being dissolved in 1 ~ 10 part of hydrogen peroxide by 1 part of calcium salt, 2 ~ 32 parts of cerium salt, 5 ~ 20 parts of inorganic bases, with pH value to 10 ~ 14 of inorganic base regulator solution, is react 15 ~ 30h under the condition of 30 ~ 80 DEG C in temperature; Through suction filtration, washing, dry, be calcine 1 ~ 5h under the condition of 500 ~ 1000 DEG C in temperature, obtain the cerium oxide Ce of calcium oxide doping
1-xca
xo
2-x, x is 0.1 ~ 0.5; The Ce will obtained again
1-xca
xo
2-xmix with 10 ~ 30 parts of hydrogen peroxide, be react 5 ~ 10h under the condition of 30 ~ 80 DEG C in temperature, namely obtain the cerium oxide OH-Ce of hydroxylated calcium oxide doping
1-xca
xo
2-x, x is 0.1 ~ 0.5;
(4) OH-Ce that the band methoxyl group aramid fiber under atmosphere of inert gases, by weight, 1 part of step (2) obtained, 5 ~ 25 parts of steps (3) obtain
1-xca
xo
2-xwith 5 ~ 20 parts of inorganic acid mixing, be react under the condition of 50 ~ 100 DEG C in temperature; Reaction terminates rear taking-up fiber, through cleaning, drying, obtains the aramid fiber that the cerium oxide of hydroxylated calcium oxide doping is coated.
In technical solution of the present invention, described aramid fiber is para-aramid fiber; Described inorganic base is NaOH, potassium hydroxide; Described inert gas is nitrogen, argon gas; Described organic solvent is ethanol, acetone, n-butanol; Described calcium salt is calcium nitrate, calcium chloride; Described cerium salt is cerous nitrate, cerium chloride; Described inorganic acid is nitric acid, the phosphoric acid of mass concentration 85%, the hydrochloric acid of mass concentration 38% of mass concentration 98%.
Compared with prior art, the beneficial effect that the present invention exists is:
1, by cerium oxide OH-Ce that hydroxylated calcium oxide adulterates
1-xca
xo
2-xreact with band methoxyl group aramid fiber, obtained modification of aramid fiber, there is chemical bonding in inorganic particulate and aramid fiber surface, therefore the Long-Time Service of modified fibre is good.
2, the cerium oxide Ce of calcium oxide doping
1-xca
xo
2-xuV absorption wide ranges, good stability, can play for a long time and absorb ultraviolet effect, and to macromolecule without degradation.
3, the cerium oxide OH-Ce adopting hydroxylated calcium oxide to adulterate
1-xca
xo
2-xbe grafted on aramid fiber, the existence of great amount of hydroxy group improves the surface-activity of aramid fiber, contributes to bonding and the infiltration of itself and resin.
4, the cerium oxide of calcium oxide doping has repaired the blemish of fiber, improves the tensile strength of fiber.In addition, the cerium oxide of calcium oxide doping itself has the heat resistance being much better than aramid fiber itself, and is coated on fiber surface, resists the transmission of heat, thus improves the heat resistance of fiber.
5, the present invention is simple to operate, and security is high, and cost is low, and agents useful for same is low toxicity or innocuous substance.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention provide cerium oxide, cerium oxide after hydroxylating, the cerium oxide of calcium oxide doping, calcium oxide doping after hydroxylating X-ray diffraction (XRD) spectrogram of cerium oxide;
Fig. 2 is the modification of aramid fiber of the Surface coating inorganic nano-particle that the embodiment of the present invention provides and the infrared spectrum of original aramid fiber contrast;
Fig. 3 is the modification of aramid fiber of the Surface coating inorganic nano-particle that the embodiment of the present invention provides and scanning electronic microscope (SEM) figure of original aramid fiber contrast;
Fig. 4 is the modification of aramid fiber of the Surface coating inorganic nano-particle that the embodiment of the present invention provides and the comparison diagram of the tensile property of original aramid fiber respectively before and after ultraviolet light irradiation.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment one
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 120mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 12h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) 14.9g cerium chloride and 1.11g calcium chloride are added in 150mL deionized water dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with the pH to 12 of NaOH regulator solution; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8.The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.8ca
0.2o
1.8.X-ray diffraction (XRD) spectrogram of the cerium oxide that the cerium oxide of calcium oxide doping and hydroxylated calcium oxide adulterate is see accompanying drawing 1.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 0.595g step (4) obtain
0.8ca
0.2o
1.8, 1g mass concentration is the mixed in hydrochloric acid of 38%, back flow reaction 6h at 65 DEG C, obtain the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, be designated as Ce
0.8ca
0.2o
1.8@KF1.Its infrared spectrum, scanning electronic microscope (SEM) photo are respectively see accompanying drawing 2,3, and surface contact angle and free energy are in table 1.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295 ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.8ca
0.2o
1.8@KF1 fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.8ca
0.2o
1.8@KF1.
Ce prepared by original aramid fiber, the present embodiment
0.8ca
0.2o
1.8the tensile property of@KF1 fiber and the fiber after 24h ultraviolet irradiation is shown in Fig. 4.
Embodiment two
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 14.6g NaOH stirring and dissolving in 120mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 3h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 20mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 180mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 20h at 50 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 14.9g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 10g NaOH, after generating precipitation, then drip 5mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 600 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 30 DEG C, reacts 10h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.8ca
0.2o
1.8.
(5) the OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 0.595g step (4) obtain
0.8ca
0.2o
1.8, 1g mass concentration be 38% nitric acid mixing, back flow reaction 6h at 65 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.8ca
0.2o
1.8@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.8ca
0.2o
1.8@KF.
Embodiment three
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 14.7g potassium hydroxide stirring and dissolving in 110mL ethanol, obtain the ethanolic solution of potassium hydroxide; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this potassium hydroxide, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL n-butanol solvent to add 250mL there-necked flask; back flow reaction 12h at 80 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 35.53g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 5mL hydrogen peroxide, and with NaOH regulator solution pH to 11; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.9ca
0.1o
1.9; The cerium oxide that calcium oxide adulterates is mixed with 30mL hydrogen peroxide, at 80 DEG C, reacts 5h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.9ca
0.1o
1.9.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 0.595g step (4) obtain
0.9ca
0.1o
1.9, 1g mass concentration be 98% nitric acid mixing, back flow reaction 6h at 65 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.9ca
0.1o
1.9@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and ultraviolet lamp tube wavelength is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.9ca
0.1o
1.9@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.9ca
0.1o
1.9@KF.
Embodiment four
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 120mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 12h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 14.9g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.8ca
0.2o
1.8.X-ray diffraction (XRD) spectrogram of the cerium oxide that the cerium oxide of calcium oxide doping and hydroxylated calcium oxide adulterate is see Fig. 1.
(5) OH-Ce that band methoxyl group aramid fiber 0.1g step (3) obtained, 1.197g step (4) obtain
0.8ca
0.2o
1.8, 1g mass concentration be 38% nitric acid mixing, back flow reaction 6h at 65 DEG C, obtains the aramid fiber of cerium oxide of coated hydroxylating calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8@KF2.Accompanying drawing 2,3 is shown in respectively by its infrared spectrum, scanning electronic microscope (SEM) photo, and surface contact angle and free energy are in table 1.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and ultraviolet lamp tube wavelength is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.8ca
0.2o
1.8@KF2 fiber carries out 24h irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.8ca
0.2o
1.8@KF2.
Ce prepared by original aramid fiber, the present embodiment
0.8ca
0.2o
1.8the tensile property of@KF2 fiber and the fiber after 24h ultraviolet irradiation is shown in Fig. 4.
Embodiment five
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10g NaOH stirring and dissolving in 100mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 8h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under argon atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 18mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL n-butanol solvent to add 250mL there-necked flask; back flow reaction 12h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 10.56g cerous nitrate, 1.64g calcium nitrate, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 10g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 600 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.9ca
0.1o
1.9; The cerium oxide that calcium oxide adulterates is mixed with 1mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.9ca
0.1o
1.9.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 0.5g step (4) obtain
0.9ca
0.1o
1.9, 1g mass concentration be 85% phosphoric acid mixing, back flow reaction 6h at 65 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.9ca
0.1o
1.9@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.9ca
0.1o
1.9@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.9ca
0.1o
1.9@KF.
Embodiment six
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 20g potassium hydroxide stirring and dissolving in 120mL ethanol, obtain the ethanolic solution of potassium hydroxide; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this potassium hydroxide, back flow reaction 3h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 10h at 100 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 14.9g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 10; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 500 DEG C of calcining 5h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 40 DEG C, reacts 8h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.8ca
0.2o
1.8.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1.0g step (4) obtain
0.8ca
0.2o
1.8, 2g mass concentration be 38% nitric acid mixing, back flow reaction 6h at 65 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.8ca
0.2o
1.8@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.8ca
0.2o
1.8@KF.
Embodiment seven
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 120mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 190mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 18h at 80 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 23.76g cerous nitrate, 1.11g calcium nitrate, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 22.2g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 1000 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.9ca
0.1o
1.9; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide OH-Ce of hydroxylated calcium oxide doping
0.9ca
0.1o
1.9.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 2.5g step (4) obtain
0.9ca
0.1o
1.9, 2g mass concentration be 98% nitric acid mixing, back flow reaction 6h at 65 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.9ca
0.2o
1.8@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.9ca
0.1o
1.9@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.9ca
0.1o
1.9@KF.
Embodiment eight
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 120mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 12h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 14.9g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.8ca
0.2o
1.8.X-ray diffraction (XRD) spectrogram of the cerium oxide of the cerium oxide of calcium oxide doping, the doping of hydroxylated calcium oxide is see accompanying drawing 1.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1.8g step (4) obtain
0.8ca
0.2o
1.8, 1g mass concentration be 38% nitric acid mixing, back flow reaction 6h at 65 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8@KF3.Its infrared spectrum, scanning electronic microscope (SEM) photo are respectively see accompanying drawing 2,3, and surface contact angle and free energy are in table 1.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm) irradiation 24h, obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.8ca
0.2o
1.8@KF3 fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.8ca
0.2o
1.8@KF3.
Ce prepared by former aramid fiber, the present embodiment
0.8ca
0.2o
1.8the tensile property of@KF3 fiber and the fiber after 24h ultraviolet irradiation is shown in Fig. 4.
See accompanying drawing 1, it is the Ce of synthesis in embodiment one, four, eight
0.8ca
0.2o
1.8and OH-Ce
0.8ca
0.2o
1.8x-ray diffraction (XRD) spectrogram.As can be seen from the figure, all diffraction maximums are all CeO
2the characteristic peak of cubic fluorite structure, illustrates the CeO that CaO adulterates
2for phase structure, generation is not had to be separated and phase in version, Ca
2+doped and substituted Ce
4+position, define solid solution.But after CaO doping, there is skew slightly and (be about 0.14 in peak to little angular direction
o), reduce according to Bragg diffraction law 2dsin θ=n λ (d is interplanar distance, and λ is incident wavelength, and θ is the angle of diffraction), θ, d increases, and this illustrates that the doping of CaO causes CeO
2the expansion of lattice, demonstrates Ce
0.8ca
0.2o
1.8successful synthesis.
See accompanying drawing 2, it is the infrared spectrum of original aramid fiber and embodiment one, embodiment four, embodiment eight modified fibre.As can be seen from the figure, embodiment one, four, six is all at 1105cm
-1occurred obvious new characteristic peak, this characteristic peak belongs to the stretching vibration of Si-O in coupling agent, illustrates that γ-glycidyl ether oxygen propyl trimethoxy silicane is successfully connected to fiber surface; At 509cm
-1locate new characteristic peak and belong to CeO
2the stretching vibration of middle Ce-O, these characteristic peaks illustrate and adopt technical scheme of the present invention, and nano particle is successfully connected to fiber surface by coupling agent, and namely nano particle is coated on aramid fiber surface with the form of chemical bond.
See Fig. 3, it is scanning electronic microscope (SEM) figure of original aramid fiber, embodiment one, embodiment four, embodiment eight.As can be seen from Fig., original aramid fiber surface fineness is before modified higher, does not have other attachment; The fiber surface modified through embodiment one, embodiment four, embodiment eight becomes coarse.In embodiment one during fiber-reactive, there is the appearance of fine particle on surface, but level of coverage is not high; In embodiment four, uniform particles ground covers fiber surface, forms fine and close integument; In embodiment eight, the grain graininess of fiber surface is no longer even, and agglomeration is comparatively obvious, and level of coverage does not also reduce.This may be that because its surface energy is comparatively large, active force to each other strengthens, thus causes the generation of reunion owing to raising along with adding nanoparticle content.
See Fig. 4, it is original aramid fiber and embodiment one, embodiment four, the tensile property comparison diagram of embodiment eight fiber before and after 24h ultraviolet irradiation.As can be seen from the figure, embodiment one and the modified TENSILE STRENGTH of embodiment four higher than pristine fibre by 8.5% and 12.4% respectively, this mainly because nano particle covered fiber, has repaired the blemish of fiber, the tensile property of fiber is promoted.The TENSILE STRENGTH of the fiber that embodiment eight obtains reduces, and may be because nano particle have impact on its mechanical property in the reunion of fiber surface.It can also be seen that from figure after 24h ultraviolet irradiation, the TENSILE STRENGTH of original aramid fiber have dropped 14.5%, and embodiment one, four, eight have dropped 0.25%, 1.3%, 1.1% respectively, which illustrate the TENSILE STRENGTH that embodiment one, four not only increases fiber, and make it decline slowly at ultraviolet irradiation environment Tensile strength.Although and embodiment eight makes the TENSILE STRENGTH of fiber decline to some extent when modification, it is also useful to the resistance to ultraviolet irradiation of fiber.
See table 1, it is original aramid fiber and embodiment one (Ce
0.8ca
0.2o
1.8@KF1), embodiment four (Ce
0.8ca
0.2o
1.8@KF2), embodiment eight (Ce
0.8ca
0.2o
1.8@KF3) surface contact angle of modified fibre and free energy.As can be seen from Table 1, adopt the surface energy of the fiber after the present invention's parcel to bring up to 21.87 mN/m from 15.17 original mN/m are maximum, improve 44%, illustrate that the present invention significantly can improve the surface-activity of fiber.
Table 1
In sum, the aramid fiber of Surface coating nano particle disclosed by the invention not only has excellent ultra-violet resistance energy, and effectively improves the surface-activity of fiber.
Embodiment nine
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 100mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under argon atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 38mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 127mL acetone to add 250mL there-necked flask; back flow reaction 16h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 8.69g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 5.55g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.7ca
0.3o
1.7.The cerium oxide that calcium oxide adulterates is mixed with 10mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.7ca
0.3o
1.7.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 0.595g step (4) obtain
0.7ca
0.3o
1.7, 0.5g mass concentration be 38% nitric acid mixing, back flow reaction 6h at 50 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.7ca
0.3o
1.7@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.7ca
0.3o
1.7@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.7ca
0.3o
1.7@KF.
Embodiment ten
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 120mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 12h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 5.58g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.6ca
0.4o
1.6; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.6ca
0.4o
1.6.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 0.595g step (4) obtain
0.6ca
0.4o
1.6, 1g mass concentration be 38% nitric acid mixing, back flow reaction 5h at 100 DEG C, obtains the aramid fiber of coated hydroxylating calcium oxide doped cerium oxide, is designated as Ce
0.6ca
0.4o
1.6@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.6ca
0.4o
1.6@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.6ca
0.4o
1.6@KF.
Embodiment 11
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 110mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 12h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 3.725g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 15h at 40 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.5ca
0.5o
1.5; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 50 DEG C, reacts 7h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.5ca
0.5o
1.5.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1.5g step (4) obtain
0.5ca
0.5o
1.5, 0.5g mass concentration be 38% nitric acid mixing, back flow reaction 15h at 50 DEG C, obtains the aramid fiber of cerium oxide of coated hydroxylating calcium oxide doping, is designated as Ce
0.5ca
0.5o
1.5@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.5ca
0.5o
1.5@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.5ca
0.5o
1.5@KF.
Embodiment 12
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 120mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL anhydrous ethanol solvent to add 250mL there-necked flask; back flow reaction 12h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 3.725g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 30h at 30 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.5ca
0.5o
1.5; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.5ca
0.5o
1.5.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1g step (4) obtain
0.5ca
0.5o
1.5, 1.5g mass concentration be 38% nitric acid mixing, back flow reaction 10h at 65 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.5ca
0.5o
1.5@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.5ca
0.5o
1.5@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.5ca
0.5o
1.5@KF.
Embodiment 13
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 105mL deionized water, obtain the aqueous solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the aqueous solution of this NaOH, back flow reaction 4h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL normal propyl alcohol solvent to join 250mL there-necked flask; back flow reaction 12h at 70 DEG C, obtains the aramid fiber of surface with methoxyl group.
(4) by 8.69g cerium chloride, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 15h at 80 DEG C after.After grinding, at 700 DEG C of calcining 1h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.7ca
0.3o
1.7; The cerium oxide that calcium oxide adulterates is mixed with 20mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.7ca
0.3o
1.7.
(5) the OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1g step (4) obtain
0.7ca
0.3o
1.7, 2g mass concentration be 85% phosphoric acid mixing, back flow reaction 5h at 80 DEG C, obtains the aramid fiber of cerium oxide of hydroxylated calcium oxide doping, is designated as Ce
0.7ca
0.3o
1.7@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.7ca
0.3o
1.7@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.7ca
0.3o
1.7@KF.
Embodiment 14
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 110mL deionized water, obtain the aqueous solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the aqueous solution of this NaOH, back flow reaction 7h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under argon atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 150mL anhydrous ethanol solvent back flow reaction 12h at 70 DEG C, obtain the aramid fiber of surface with methoxyl group.
(4) by 10.56g cerous nitrate, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 11; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 700 DEG C of calcining 3h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.8ca
0.2o
1.8.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1g step (4) obtain
0.8ca
0.2o
1.8, 1.2g mass concentration be 98% nitric acid mixing, back flow reaction 10h at 65 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.8ca
0.2o
1.8@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.8ca
0.2o
1.8@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.8ca
0.2o
1.8@KF.
Embodiment 15
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 10.5g NaOH stirring and dissolving in 100mL ethanol, obtain the ethanolic solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 20mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 130mL anhydrous ethanol solvent back flow reaction 12h at 100 DEG C, obtain the aramid fiber of surface with methoxyl group.
(4) by 6.16g cerous nitrate, 1.11g calcium chloride, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 6g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 15h at 80 DEG C after.After grinding, at 700 DEG C of calcining 5h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.7ca
0.3o
1.7; The cerium oxide that calcium oxide adulterates is mixed with 20mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.7ca
0.3o
1.7.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1g step (4) obtain
0.7ca
0.3o
1.7, 1.8g mass concentration be 38% nitric acid mixing, back flow reaction 8h at 70 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.7ca
0.3o
1.7@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.7ca
0.3o
1.7@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.7ca
0.3o
1.7@KF.
Embodiment 16
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 15.75g NaOH stirring and dissolving in 100mL deionized water, obtain the aqueous solution of NaOH; The KF fiber that 0.1g step (1) obtains is immersed in the aqueous solution of this NaOH, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 30mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 160mL anhydrous ethanol solvent back flow reaction 12h at 70 DEG C, obtain the aramid fiber of surface with methoxyl group.
(4) by 3.96g cerous nitrate, 1.11g calcium nitrate, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 8g NaOH, after generating precipitation, then drip 3mL hydrogen peroxide, and with NaOH regulator solution pH to 14; Suction filtration, washing, 120 DEG C of dryings react 20h at 60 DEG C after.After grinding, at 800 DEG C of calcining 5h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.6ca
0.4o
1.6; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.6ca
0.4o
1.6.
(5) OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1g step (4) obtain
0.6ca
0.4o
1.6, 0.5g mass concentration be 85% phosphoric acid mixing, back flow reaction 8h at 70 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.6ca
0.4o
1.6@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.6ca
0.4o
1.6@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.6ca
0.4o
1.6@KF.
Embodiment 17
1. the preparation of the aramid fiber of Surface coating inorganic nano-particle
(1) by 0.5g para-aramid fiber (Kevlar-49, diameter 12um, density 1.43g/cm
3, du pont company produces) be immersed in acetone, benzinum, deionized water respectively, each 3 hours of backflow cleaning; Cleaning terminates rear taking-up fiber, and dry 12h at being placed on 80 DEG C, obtains clean aramid fiber, be designated as KF.
(2) by 14.7g potassium hydroxide stirring and dissolving in 100mL ethanol, obtain the ethanolic solution of potassium hydroxide; The KF fiber that 0.1g step (1) obtains is immersed in the ethanolic solution of this potassium hydroxide, back flow reaction 5h; Reaction terminates after washing, drying, obtains the fiber of surface with amino.
(3) under nitrogen atmosphere protection; get 0.1g step (2) to obtain being with amino aramid fiber, 20mL γ-glycidyl ether oxygen propyl trimethoxy silicane, 130mL anhydrous ethanol solvent back flow reaction 12h at 70 DEG C, obtain the aramid fiber of surface with methoxyl group.
(4) by 2.64g cerium chloride, 1.11g calcium nitrate, add in 150mL deionized water and dissolve, obtain the mixed solution of cerium chloride and calcium chloride; In mixed solution, add 10g NaOH, after generating precipitation, then drip 10mL hydrogen peroxide, and with NaOH regulator solution pH to 12; Suction filtration, washing, 120 DEG C of dryings react 20h at 40 DEG C after.After grinding, at 600 DEG C of calcining 5h, obtain milk yellow powder, i.e. the cerium oxide of calcium oxide doping, is designated as Ce
0.5ca
0.5o
1.5; The cerium oxide that calcium oxide adulterates is mixed with 15mL hydrogen peroxide, at 60 DEG C, reacts 6h, obtain the cerium oxide of hydroxylated calcium oxide doping, be designated as OH-Ce
0.5ca
0.5o
1.5.
(5) the OH-Ce that the aramid fiber of band methoxyl group 0.1g step (3) obtained, 1g step (4) obtain
0.5ca
0.5o
1.5, 1.5g mass concentration be 38% nitric acid mixing, back flow reaction 6h at 60 DEG C, obtains the aramid fiber of the cerium oxide of coated hydroxylated calcium oxide doping, is designated as Ce
0.5ca
0.5o
1.5@KF.
2. the ultraviolet irradiation of fiber
Original aramid fiber is placed in culture dish, is placed in irradiation 24h in uviol lamp weather-resistant test box (temperature is 60 DEG C, and humidity is 60%, and the wavelength of ultraviolet lamp tube is at 295nm ~ 360nm), obtains 24h ultraviolet irradiation fiber, be designated as UV-KF.
According to above-mentioned same steps and condition, to the Ce that above-mentioned steps (5) obtains
0.5ca
0.5o
1.5@KF fiber carries out 24h ultraviolet irradiation, obtains 24h ultraviolet irradiation fiber, is designated as UV-Ce
0.5ca
0.5o
1.5@KF.
Claims (8)
1. a preparation method for the aramid fiber of Surface coating inorganic nano-particle, is characterized in that comprising the steps:
(1) by weight, 1 part of aramid fiber is immersed in reactant liquor, described reactant liquor comprises 100 ~ 200 parts of inorganic bases and 800 ~ 950 parts of alcohol or deionized water, be react under the condition of 40 ~ 80 DEG C in temperature, reaction terminates rear taking-up fiber, through cleaning, dry, obtain being with amino aramid fiber;
(2) under atmosphere of inert gases, by weight, the aramid fiber of 1 part of band amino, 200 ~ 400 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes and 1000 ~ 1500 parts of organic solvents are placed in reaction vessel, be react 10 ~ 20h under the condition of 50 ~ 100 DEG C in temperature, obtain the aramid fiber being with methoxyl group;
(3) by weight, being dissolved in 1 ~ 10 part of hydrogen peroxide by 1 part of calcium salt, 2 ~ 32 parts of cerium salt, 5 ~ 20 parts of inorganic bases, with pH value to 10 ~ 14 of inorganic base regulator solution, is react 15 ~ 30h under the condition of 30 ~ 80 DEG C in temperature; Through suction filtration, washing, dry, be calcine 1 ~ 5h under the condition of 500 ~ 1000 DEG C in temperature, obtain the cerium oxide Ce of calcium oxide doping
1-xca
xo
2-x, x is 0.1 ~ 0.5; The Ce will obtained again
1-xca
xo
2-xmix with 10 ~ 30 parts of hydrogen peroxide, be react 5 ~ 10h under the condition of 30 ~ 80 DEG C in temperature, namely obtain the cerium oxide OH-Ce of hydroxylated calcium oxide doping
1-xca
xo
2-x, x is 0.1 ~ 0.5;
(4) OH-Ce that the band methoxyl group aramid fiber under atmosphere of inert gases, by weight, 1 part of step (2) obtained, 5 ~ 25 parts of steps (3) obtain
1-xca
xo
2-xwith 5 ~ 20 parts of inorganic acid mixing, be react under the condition of 50 ~ 100 DEG C in temperature; Reaction terminates rear taking-up fiber, through cleaning, drying, obtains the aramid fiber that the cerium oxide of hydroxylated calcium oxide doping is coated.
2. the preparation method of the aramid fiber of Surface coating inorganic nano-particle according to claim 1, is characterized in that: described aramid fiber is para-aramid fiber.
3. the preparation method of the aramid fiber of Surface coating inorganic nano-particle according to claim 1, is characterized in that: described inorganic base is NaOH, potassium hydroxide.
4. the preparation method of the aramid fiber of Surface coating inorganic nano-particle according to claim 1, is characterized in that: described inert gas is nitrogen, argon gas.
5. the preparation method of the aramid fiber of Surface coating inorganic nano-particle according to claim 1, is characterized in that: described organic solvent is ethanol, acetone, n-butanol.
6. the preparation method of the aramid fiber of Surface coating inorganic nano-particle according to claim 1, is characterized in that: described calcium salt is calcium nitrate, calcium chloride.
7. the preparation method of the aramid fiber of Surface coating inorganic nano-particle according to claim 1, is characterized in that: described cerium salt is cerous nitrate, cerium chloride.
8. the preparation method of the aramid fiber of Surface coating inorganic nano-particle according to claim 1, is characterized in that: described inorganic acid is nitric acid, the phosphoric acid of mass concentration 85%, the hydrochloric acid of mass concentration 38% of mass concentration 98%.
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| CN105332275B (en) * | 2014-05-30 | 2019-07-12 | 东丽纤维研究所（中国）有限公司 | A kind of para-aramid fiber |
| CN105862396B (en) * | 2016-05-05 | 2018-03-23 | 苏州大学 | A kind of surface modification of aramid fiber and preparation method thereof |
| CN108642862B (en) * | 2018-05-04 | 2020-04-03 | 苏州大学 | Surface modified aramid fiber and preparation method thereof |
| WO2020124396A1 (en) * | 2018-12-18 | 2020-06-25 | 南通纺织丝绸产业技术研究院 | Flame-retardant ultraviolet-resistant aramid fiber |
| CN109650815A (en) * | 2019-01-21 | 2019-04-19 | 北京通成达水务建设有限公司 | Anti-crack concrete |
| CN110553546B (en) * | 2019-09-27 | 2021-08-20 | 东华大学 | Method for preparing composite stab-resistant sheet by layered bedding and fusion casting of inorganic particles and waste fabrics and application |
| CN111118881B (en) * | 2020-01-17 | 2022-04-05 | 超美斯新材料股份有限公司 | Nano-zinc oxide modified aramid fiber and preparation method thereof |
| CN115012204B (en) * | 2022-06-24 | 2023-09-15 | 佛山(华南)新材料研究院 | Composite bactericidal fiber material and preparation method thereof |
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